WO2018181222A1 - 熱可塑性液晶ポリマーおよびそのフィルム - Google Patents

熱可塑性液晶ポリマーおよびそのフィルム Download PDF

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Publication number
WO2018181222A1
WO2018181222A1 PCT/JP2018/012219 JP2018012219W WO2018181222A1 WO 2018181222 A1 WO2018181222 A1 WO 2018181222A1 JP 2018012219 W JP2018012219 W JP 2018012219W WO 2018181222 A1 WO2018181222 A1 WO 2018181222A1
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WIPO (PCT)
Prior art keywords
liquid crystal
crystal polymer
thermoplastic liquid
group
repeating unit
Prior art date
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PCT/JP2018/012219
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English (en)
French (fr)
Japanese (ja)
Inventor
貴文 今野
砂本　辰也
南葉　道之
原　哲也
Original Assignee
株式会社クラレ
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Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to CN201880020206.7A priority Critical patent/CN110446738B/zh
Priority to KR1020197027852A priority patent/KR102612138B1/ko
Priority to JP2019509835A priority patent/JP7069124B2/ja
Priority to EP18778136.4A priority patent/EP3604381B1/en
Publication of WO2018181222A1 publication Critical patent/WO2018181222A1/ja
Priority to US16/577,105 priority patent/US11674083B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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    • B32B7/02—Physical, chemical or physicochemical properties
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
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    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
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    • C—CHEMISTRY; METALLURGY
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    • H—ELECTRICITY
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Definitions

  • the present invention relates to a thermoplastic polymer capable of forming an optically anisotropic melt phase (hereinafter referred to as a thermoplastic liquid crystal polymer). More specifically, the present invention relates to a thermoplastic liquid crystal polymer that can reduce a dielectric loss tangent in a high frequency band and suppresses an increase in melting point.
  • millimeter wave radars used for detecting distances between vehicles for safe driving assistance and automatic driving of automobiles are being developed.
  • the millimeter wave radar includes an antenna for transmitting and receiving an electromagnetic wave signal.
  • a material having a low dielectric loss tangent in a high frequency band is particularly required for an insulating substrate used for the antenna.
  • Ceramic substrates and fluorine substrates are known as antenna insulating substrates.
  • ceramic substrates are difficult to process and are expensive, and fluorine substrates use glass that is used to increase dimensional stability. Due to the influence of cloth or the like, there is a problem in high-frequency characteristics and moisture resistance of the entire substrate.
  • thermoplastic liquid crystal polymers are attracting attention as materials having excellent high-frequency characteristics.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2009-108190 discloses a repeating unit derived from 6-hydroxy-2-naphthoic acid, a repeating unit derived from 4,4′-dihydroxybiphenyl, and an aromatic dicarboxylic acid at a specific ratio.
  • wholly aromatic liquid crystal polyesters containing repeating units derived from acids wholly aromatic liquid crystal polyesters containing repeating units derived from a small amount of benzenediol are disclosed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-196930 discloses 30 to 80 mol% of repeating units derived from 2-hydroxy-6-naphthoic acid, 35 to 10 mol% of repeating units derived from an aromatic diol, and aromatics.
  • An aromatic liquid crystal polyester substantially comprising 35 to 10 mol% of repeating units derived from an aromatic dicarboxylic acid is disclosed.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2005-272810 discloses that 40 to 74.8 mol% of repeating units derived from 2-hydroxy-6-naphthoic acid and 12.1 of repeating units derived from aromatic diol. 5 to 30 mol%, 12.5 to 30 mol% of repeating units derived from naphthalenedicarboxylic acid and 0.2 to 15 mol% of repeating units derived from aromatic dicarboxylic acid, derived from aromatic dicarboxylic acid An aromatic liquid crystal polyester in which the number of moles of repeating units derived from naphthalenedicarboxylic acid is larger than that of repeating units is disclosed.
  • Patent Document 1 describes that the wholly aromatic liquid crystalline polyester has excellent mechanical properties and excellent dielectric properties in a high frequency band, but is processed into a dumbbell-shaped test piece or a stick-shaped test piece by injection molding. Since the strength characteristics and dielectric loss tangent are examined, the processability as a film and the dielectric loss tangent when used as a film are not known.
  • Patent Document 2 aims to improve dielectric loss in the megahertz band, further reduction in the dielectric loss tangent in the high frequency band is desired.
  • Patent Document 3 describes that an aromatic liquid crystal polyester having an excellent balance between heat resistance and film processability and low dielectric loss is obtained.
  • the melting point increases due to a trade-off with heat resistance. Therefore, a further low dielectric loss tangent is desired.
  • an object of the present invention is to provide a thermoplastic liquid crystal polymer capable of reducing the dielectric loss tangent in the high frequency band and suppressing the rise in melting point.
  • Another object of the present invention is to provide a thermoplastic liquid crystal polymer film having a very low dielectric loss tangent in a high frequency band.
  • the inventors of the present invention have made extensive studies in order to achieve the above object, and as a result, (1) focusing on the carbonyl group constituting the permanent dipole in the thermoplastic liquid crystal polymer, and examining the orientation and rotational properties thereof.
  • the rotational energy of the carbonyl group is increased by setting the repeating unit in which the aromatic ring bonded to the carbonyl group is a bulky naphthalene ring within a predetermined range of the total repeating units of the thermoplastic liquid crystal polymer. It has been found that the dielectric loss tangent of the thermoplastic liquid crystal polymer can be made extremely low because the rotational motion component decreases in the gigahertz band.
  • thermoplastic liquid crystal polymer capable of forming an optically anisotropic melt phase
  • a thermoplastic liquid crystal polymer Including repeating units represented by the following formulas (I), (II), (III) and (IV),
  • the molar ratio of the total amount of repeating units represented by formula (I) and formula (II) to the total amount of all repeating units in the thermoplastic liquid crystal polymer is 50 to 90 mol% (preferably 55 to 85 mol%, more Preferably 60 to 80 mol%)
  • Ar 1 and Ar 2 are divalent aromatic groups different from each other
  • thermoplastic liquid crystal polymer according to aspect 1 wherein the molar ratio of the repeating unit represented by formula (I) to the repeating unit represented by formula (II) is 45/55 to 90 / Thermoplastic liquid crystal polymer of 10 (more preferably 55/45 to 85/15, still more preferably 60/40 to 80/20).
  • thermoplastic liquid crystal polymer according to aspect 1 or 2 wherein the molar ratio of the repeating unit represented by the formula (II) to the total total amount of the repeating units derived from dicarboxylic acid in the thermoplastic liquid crystal polymer is 85 mol%.
  • thermoplastic liquid crystal polymer of the above or more (preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, particularly preferably 100 mol%).
  • thermoplastic liquid crystal polymer according to any one of aspects 1 to 4, wherein the repeating units represented by formulas (III) and (IV) are hydroquinone, 4,4′-dihydroxybiphenyl, phenylhydroquinone, and A thermoplastic liquid crystal polymer which is a repeating unit derived from two kinds of aromatic diols selected from 4,4′-dihydroxydiphenyl ether.
  • thermoplastic liquid crystal polymer according to any one of aspects 1 to 5, wherein the temperature difference between the melting point and the solidification temperature is in the range of 40 to 160 ° C (more preferably 45 to 155 ° C). .
  • thermoplastic liquid crystal polymer film comprising the thermoplastic liquid crystal polymer according to any one of aspects 1 to 6.
  • a circuit board comprising at least one conductor layer and the thermoplastic liquid crystal polymer film according to the aspect 7 or 8.
  • An on-vehicle radar including the circuit board according to any one of aspects 10 to 12.
  • the present invention can provide a thermoplastic liquid crystal polymer that can not only have a very low dielectric loss tangent but also can suppress an increase in melting point.
  • the film composed of the thermoplastic liquid crystal polymer of the present invention has a very low dielectric loss tangent in the high frequency band, it can be suitably used as a member (for example, a millimeter wave antenna member) constituting an in-vehicle radar. .
  • thermoplastic liquid crystal polymer contains at least a specific proportion of repeating units represented by the following formulas (I), (II), (III) and (IV).
  • Ar 1 and Ar 2 are divalent aromatic groups different from each other
  • Examples of the monomer that gives the repeating unit represented by the formula (I) include 6-hydroxy-2-naphthoic acid and its derivatives.
  • Examples of the monomer that gives the repeating unit represented by the formula (II) include 2,6-naphthalenedicarboxylic acid and derivatives thereof.
  • the derivative includes, for example, an ester-forming derivative such as an acylated product, an ester derivative, and an acid halide.
  • the name of the compound includes the derivative.
  • thermoplastic liquid crystal polymer of the present invention from the viewpoint of keeping the dielectric loss tangent in the gigahertz band low, the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) with respect to the total amount of all repeating units.
  • the molar ratio of the total amount is 50 to 90 mol%.
  • Esters that are permanent dipoles in a thermoplastic liquid crystal polymer by setting the molar ratio of the total amount of repeating units in which the aromatic ring bonded to the carbonyl group is a bulky naphthalene ring to the total amount of all repeating units within this range. Because the rotational energy of the carbonyl group of the bond can be increased, it is possible to suppress an increase in dielectric loss tangent resulting from dissipation to thermal energy due to the rotational motion of the permanent dipole.
  • the molar ratio of the total amount of the repeating unit represented by formula (I) and the repeating unit represented by formula (II) with respect to the total amount of all repeating units is preferably 55 to 85 mol%, more preferably 60 to 80%. It may be mol%. If the molar ratio of the total amount of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) with respect to the total amount of all repeating units is less than 50 mol%, the dielectric loss tangent is increased, which is not preferable. .
  • the molar ratio of the repeating unit represented by the formula (I) with respect to the total amount of repeating units derived from hydroxycarboxylic acid in the thermoplastic liquid crystal polymer is For example, it may be 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and particularly preferably 100 mol%. .
  • the molar ratio of the repeating unit represented by the formula (II) with respect to the total total amount of repeating units derived from dicarboxylic acid in the thermoplastic liquid crystal polymer is: For example, it may be 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and particularly preferably 100 mol%.
  • repeating units represented by formula (III) and formula (IV) are repeating units derived from different divalent aromatic diols.
  • the repeating unit derived from the aromatic diol constituting the thermoplastic liquid crystal polymer into two types having different structures, the blending ratio of the repeating unit derived from the two types of aromatic diol is in a specific range, thereby strengthening An increase in the melting point can be suppressed because it is difficult to form a proper crystal structure.
  • the molar ratio of the repeating unit represented by the formula (III) to the repeating unit represented by the formula (IV) is preferably 25/75 to 75/25, more preferably 30/70 to 70/30, particularly preferably 35. / 65 to 65/35 may be used.
  • Ar 1 and Ar 2 are different from each other, and 1,4-phenylene, 1,3-phenylene, 1,5-naphthylene, 2,6- A group selected from the group consisting of naphthylene, 4,4′-biphenylene, 2,6-anthraquinonylene, and a divalent residue having two or more phenylenes linked by a linking group at the para position,
  • the linking group may be selected from the group consisting of a carbon-carbon bond, an oxy group, an alkylene group having 1 to 3 carbon atoms, an amino group, a carbonyl group, a sulfide group, a sulfinyl group, and a sulfonyl group. These may optionally have a substituent (for example, a lower alkyl group such as a C 1-3 alkyl group, a halogen atom, a phenyl group, etc.).
  • Examples of the monomer that gives the repeating unit represented by formulas (III) and (IV) include aromatic diol compounds selected from the group exemplified in Table 1 below and derivatives thereof.
  • the monomer giving the repeating unit represented by formulas (III) and (IV) is selected from linear aromatic diol compounds.
  • the linear aromatic diol compound is preferably an aromatic diol compound in which the portion forming the main chain of the thermoplastic liquid crystal polymer is linear (for example, para-position or 2,6-position).
  • Ar 1 and Ar 2 are different from each other, and 1,4-phenylene, 2,6-naphthylene, 4,4′-biphenylene, 2, A group selected from the group consisting of 6-anthraquinonylene and a group selected from divalent residues of phenylene number 2 linked by a linking group at the para position, wherein the linking group is carbon-carbon It may be selected from the group consisting of a bond, an oxy group, an alkylene group having 1 to 3 carbon atoms, and a carbonyl group, and these are optionally substituted (for example, a lower alkyl group such as a C 1-3 alkyl group, phenyl Group) and the like.
  • the inventors of the present invention have a low dielectric loss tangent without disturbing liquid crystallinity when the repeating units represented by the formulas (III) and (IV) are configured in a specific combination in the above-described thermoplastic liquid crystal polymer. I found that I can maintain it.
  • the monomers giving the repeating units represented by formulas (III) and (IV) are two types selected from hydroquinone, 4,4′-dihydroxybiphenyl, phenylhydroquinone, and 4,4′-dihydroxydiphenyl ether
  • An aromatic diol compound is preferred.
  • the molar ratio with the total amount of the repeating units represented by formulas (III) and (IV) may be, for example, 90/100 to 100/90, preferably 95/100 to 100/95, Preferably it may be 100/100.
  • thermoplastic liquid crystal polymer of the present invention contains an aliphatic diol compound such as a repeating unit derived from an HO (CH 2 ) n OH (n is an integer of 2 to 12). May be included.
  • thermoplastic liquid crystal polymer of the present invention is a repeating unit derived from a diol, a repeating unit derived from a dicarboxylic acid, and a hydroxycarboxylic acid, which are used in known thermoplastic liquid crystal polyesters, as long as the effects of the present invention can be achieved. It may contain a repeating unit derived from, a repeating unit derived from an aromatic diamine, an aromatic hydroxyamine or an aromatic aminocarboxylic acid.
  • the thermoplastic liquid crystal polymer may contain repeating units derived from compounds classified in the following Tables 2 to 4.
  • Aromatic or aliphatic dicarboxylic acids (see Table 2 for typical examples)
  • Aromatic hydroxycarboxylic acids see Table 3 for typical examples.
  • Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)
  • thermoplastic liquid crystal polymer of the present invention is not particularly limited as long as the effects of the present invention can be achieved.
  • an amide bond is introduced therein. It may also be a thermoplastic liquid crystal polyester amide.
  • the thermoplastic liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond is further introduced into an aromatic polyester or an aromatic polyester amide.
  • optically anisotropic melt phase referred to in the present invention can be formed, for example, by placing the sample on a hot stage, heating and heating in a nitrogen atmosphere, and observing the transmitted light of the sample. .
  • thermoplastic liquid crystal polymer of the present invention contains a specific amount of a repeating unit having a naphthalene skeleton, an increase in the melting point can be suppressed.
  • the melting point (hereinafter referred to as Tm 0 ) is preferably in the range of 260 to 330 ° C. (eg, 270 to 330 ° C.), more preferably Tm 0 is 270 to 320 ° C. (eg, 290 to 320 ° C.). It may be a thing.
  • thermoplastic liquid crystal polymer of the present invention Since the melting point of the thermoplastic liquid crystal polymer of the present invention is in a specific range, the temperature during melt extrusion can be lowered, the film moldability can be improved, and the thermal decomposition of the thermoplastic liquid crystal polymer can be suppressed.
  • fusing point is a value measured by the method described in the below-mentioned Example.
  • the thermoplastic liquid crystal polymer of the present invention preferably not only suppresses an increase in the melting point but also can increase the temperature difference between the melting point and the solidification temperature.
  • the temperature difference between the melting point and the solidification temperature is preferably in the range of 40 to 160 ° C, more preferably in the range of 45 to 155 ° C.
  • this temperature difference is in the above-mentioned range, when film forming the thermoplastic liquid crystal polymer in film forming, a sufficient time can be taken from the melting of the thermoplastic liquid crystal polymer to solidification. It is possible to increase the degree of freedom in setting the temperature conditions such as the film temperature.
  • the solidification temperature refers to the peak temperature of crystallization (crystallization temperature) in the cooling process of DSC measurement, and refers to the glass transition temperature when no crystallization temperature is observed. Specifically, the solidification temperature is measured by the method described in Examples described later. The temperature difference between the melting point and the solidification temperature is calculated as a difference obtained by subtracting the solidification temperature from the melting point of the thermoplastic liquid crystal polymer.
  • the thermoplastic liquid crystal polymer may be a resin composition containing other components, and the resin composition includes polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate as long as the effects of the present invention are not impaired. Further, polyamide, polyphenylene sulfide, polyether ether ketone, thermoplastic polymer such as fluororesin, and various additives may be added. Moreover, you may add a filler as needed.
  • thermoplastic liquid crystal polymer There is no restriction
  • the monomer used for polycondensation may be a direct polymerization method using 6-hydroxy-2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, various aromatic diols, and 6-hydroxy-2-naphthoic acid.
  • acylated products whose terminals are activated by acylating these hydroxy groups may be used for polymerization.
  • the monomer acylated product may be synthesized in advance by acylating the monomer, or is produced in the reaction system by adding an acylating agent to the monomer during the production of the thermoplastic liquid crystal polymer. You can also.
  • the acylating agent include acid anhydrides such as acetic anhydride.
  • Polycondensation may be carried out in the presence of various catalysts, such as organotin catalysts (dialkyltin oxides, etc.), antimony catalysts (antimony trioxide, etc.), titanium catalysts (titanium dioxide, etc.), carboxylic acids, etc.
  • organotin catalysts dialkyltin oxides, etc.
  • antimony catalysts antimony trioxide, etc.
  • titanium catalysts titanium catalysts (titanium dioxide, etc.)
  • carboxylic acids etc.
  • Alkali metal salts or alkaline earth metal salts such as potassium acetate
  • Lewis acid salts such as BF 3
  • Solid phase polymerization is a method in which the polymer obtained by the melt polymerization process is extracted, pulverized into powder or flakes, and then heat-treated in a solid phase under vacuum or in an inert atmosphere such as nitrogen. Etc.
  • thermoplastic liquid crystal polymer film Since the thermoplastic liquid crystal polymer of the present invention can suppress an increase in melting point despite containing a specific amount of repeating units having a naphthalene skeleton, a thermoplastic liquid crystal polymer film can be suitably produced.
  • the thermoplastic liquid crystal polymer film is obtained, for example, by extruding a melt-kneaded product of the thermoplastic liquid crystal polymer.
  • any method can be used, but the well-known T-die method, inflation method and the like are industrially advantageous.
  • the inflation method stress is applied not only in the mechanical axis direction of the film (hereinafter abbreviated as MD direction) but also in the direction orthogonal thereto (hereinafter abbreviated as TD direction), and is uniform in the MD direction and TD direction. Since the film can be stretched, a film in which the molecular orientation in the MD direction and the TD direction, the dielectric properties, and the like are controlled can be obtained.
  • the melt sheet extruded from the T-die may be formed by stretching simultaneously in both the MD direction and the TD direction of the film, or The melt sheet extruded from the T die may be stretched once in the MD direction and then stretched in the TD direction to form a film.
  • a predetermined draw ratio corresponding to a stretching ratio in the MD direction
  • a blow ratio corresponding to a stretching ratio in the TD direction
  • the film may be formed by stretching.
  • the draw ratio of such extrusion molding may be, for example, about 1.0 to 10, preferably about 1.2 to 7, more preferably about 1 as the draw ratio (or draw ratio) in the MD direction. It may be about 3-7. Further, the draw ratio (or blow ratio) in the TD direction may be, for example, about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.
  • thermoplastic liquid crystal polymer film may be known or conventional heat treatment to adjust the melting point and / or the thermal expansion coefficient of the thermoplastic liquid crystal polymer film.
  • the heat treatment conditions can be appropriately set according to the purpose.
  • the melting point of the thermoplastic liquid crystal polymer is Tm 0 ⁇ 10 ° C. or higher (for example, Tm 0 ⁇ 10 to Tm 0 + 30 ° C., preferably Tm 0 to Tm 0 + 20 ° C.)
  • the melting point (Tm) of the thermoplastic liquid crystal polymer film may be increased by heating for several hours.
  • thermoplastic liquid crystal polymer film which is one embodiment of the present invention is composed of the above-described thermoplastic liquid crystal polymer.
  • the thermoplastic liquid crystal polymer film has a specific amount of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II) in the repeating unit of the thermoplastic liquid crystal polymer constituting the film. Therefore, the dielectric loss tangent can be made extremely low.
  • the dielectric loss tangent at 25 ° C. and 5 GHz may be 0.0007 or less, more preferably 0.0006 or less.
  • the dielectric loss tangent is a value measured by the method described in Examples described later.
  • the dielectric loss tangent is calculated as an average value of the dielectric loss tangent at 5 GHz in the X direction and the Y direction measured in one direction (X direction) and the direction perpendicular thereto (Y direction).
  • the dielectric loss tangent in a higher frequency band can be lowered.
  • the dielectric loss tangent at 40 ° C. and 24 GHz may be 0.0012 or less, more preferably 0.0010 or less.
  • the dielectric loss tangent at 40 ° C. and 24 GHz is a value measured by the method described in the examples described later.
  • the dielectric loss tangent at a high temperature (for example, 120 ° C.) can be lowered.
  • the dielectric loss tangent at 120 ° C. and 24 GHz may be 0.0025 or less, more preferably 0.0022 or less, and still more preferably 0.0020 or less.
  • the dielectric loss tangent at 120 ° C. and 24 GHz is a value measured by the method described in the examples described later.
  • thermoplastic liquid crystal polymer film of the present invention has a very low dielectric loss tangent, it can be suitably used as a substrate material, particularly as a substrate material used in radars corresponding to the gigahertz band. Since the transmission loss becomes smaller as the dielectric loss tangent is lower, such a thermoplastic liquid crystal polymer film can be suitably used for a transmission circuit, and low power and low noise can be achieved.
  • the thermoplastic liquid crystal polymer film of the present invention may have a dielectric constant of, for example, 2.5 to 4.0 (eg, about 2.6 to 4.0) at 25 ° C. and 5 GHz, preferably 2. It may be about 8 to 4.0.
  • the dielectric constant at 40 ° C. and 24 GHz may be 2.5 to 4.0 (for example, about 2.6 to 4.0), and preferably about 2.8 to 4.0. Good.
  • the dielectric constant at 120 ° C. and 24 GHz may be 2.5 to 4.0 (for example, about 2.6 to 4.0), and preferably about 2.8 to 4.0. Good.
  • a dielectric constant is a value measured by the method described in the Example mentioned later. The dielectric constant is calculated as an average value of the dielectric tangent in the X direction and the Y direction at a predetermined frequency (and temperature) measured in one direction (X direction) and a direction orthogonal to the one direction (Y direction).
  • One configuration of the present invention may include a metal-clad laminate in which a metal layer (for example, a metal sheet) is bonded to at least one surface of the thermoplastic liquid crystal polymer film.
  • the metal layer may be a metal layer formed of, for example, gold, silver, copper, iron, nickel, aluminum, or an alloy metal thereof.
  • the metal-clad laminate may preferably be a copper-clad laminate. With respect to the metal-clad laminate, a circuit pattern can be formed on the metal layer portion by a known or conventional method to obtain a circuit board.
  • the circuit board according to the present invention includes at least one conductor layer and at least one insulator (or dielectric) layer, and uses the thermoplastic liquid crystal polymer film as an insulator (or dielectric). As long as the shape is not particularly limited, it can be used as various high-frequency circuit boards by known or conventional means.
  • the circuit board may be a circuit board (or a semiconductor element mounting board) on which a semiconductor element (for example, an IC chip) is mounted.
  • the conductor layer is formed of, for example, a metal having at least conductivity, and a circuit is formed on the conductor layer using a known circuit processing method.
  • the conductor forming the conductor layer may be various conductive metals such as gold, silver, copper, iron, nickel, aluminum, or alloy metals thereof.
  • circuit board having the configuration of the present invention is controlled to have a very low dielectric loss tangent
  • various known transmission lines such as coaxial lines, strip lines, microstrip lines, coplanar lines, and parallel lines are known or commonly used. You may use for a transmission line and may be used for an antenna (for example, antenna for microwaves or millimeter waves).
  • the circuit board may be used in an antenna device in which an antenna and a transmission line are integrated.
  • the antenna examples include an antenna using millimeter waves and microwaves such as a waveguide slot antenna, a horn antenna, a lens antenna, a printed antenna, a triplate antenna, a microstrip antenna, and a patch antenna.
  • These antennas include, for example, a circuit board (preferably a multilayer circuit board) including at least one conductor layer and at least one insulator (or dielectric) made of the thermoplastic liquid crystal polymer film of the present invention. At least as a substrate.
  • the circuit board (or semiconductor element mounting board) of the present invention is preferably used in various sensors, particularly in-vehicle radars.
  • Various sensors, particularly in-vehicle radars include, for example, a circuit board including the thermoplastic liquid crystal polymer film of the present invention, At least a semiconductor element (for example, an IC chip) is provided.
  • thermotropic liquid crystal polymer under the condition of Tm 0 + 15 ⁇ Tm 0 + 30 °C, subjected to hot pressing at a pressure of 100 kg / cm 2, to obtain a thickness 125 [mu] m, vertical 12cm, a 12cm square sheet of horizontal 12cm.
  • the obtained sheet was cut in the sheet lateral direction (X direction) to obtain a sample piece having a length of 8 cm, a width of 2 mm, and a thickness of 125 ⁇ m.
  • a sample piece having a length of 8 cm, a width of 2 mm, and a thickness of 125 ⁇ m was obtained in the same manner in the longitudinal direction of the sheet (Y direction).
  • Dielectric constant / dielectric loss tangent measurement was performed by a cavity resonator perturbation method at a frequency of 5 GHz. Connect a 5 GHz cavity resonator (manufactured by Kanto Electronics Co., Ltd.) to a network analyzer (Agilent Technology “E8362B”), insert the above sample piece into the cavity resonator, and perform measurement at 25 ° C. Average values in the vertical and horizontal directions were adopted.
  • thermotropic liquid crystal polymer under the condition of Tm 0 + 20 ⁇ Tm 0 + 30 °C, subjected to hot pressing at a pressure of 100 kg / cm 2, to obtain a thickness 1 mm, vertical 10cm, a 10cm square sheet of horizontal 10cm.
  • the obtained sheet is cut in the transverse direction of the sheet by adjusting the width (about 1.6 mm) so that the length of the diagonal line of the cross section becomes 1.87 mm, and the length is 40 mm and the width is about 1.6 mm.
  • a sample piece having a thickness of 1 mm was obtained.
  • a sample piece having a length of 40 mm, a width of about 1.6 mm, and a thickness of 1 mm was obtained in the longitudinal direction of the sheet.
  • Example 1 In a 100 mL reaction vessel, 19.74 g (60 mol%) of 6-hydroxy-2-naphthoic acid, 7.56 g (20 mol%) of 2,6-naphthalenedicarboxylic acid, 0.96 g of hydroquinone (5 mol%), 4 , 4′-dihydroxybiphenyl (4.88 g, 15 mol%), acetic anhydride (19.64 g) and potassium acetate (3.77 mg) as a polymerization catalyst were charged, and acetylated under a nitrogen atmosphere (160 ° C., refluxing for about 2 hours) After that, hold at 280 ° C. for 0.5 hour, 320 ° C. for 1 hour, 360 ° C.
  • the aromatic liquid crystal polyester was obtained by substitution.
  • the resulting thermoplastic liquid crystal polymer had a melting point of 294 ° C., a solidification temperature of 228 ° C., and a temperature difference between the melting point and the solidification temperature of 66 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • Example 2 The raw materials charged into the reactor were 20.19 g (60 mol%) of 6-hydroxy-2-naphthoic acid, 7.73 g (20 mol%) of 2,6-naphthalenedicarboxylic acid, 1.97 g (10 mol%) of hydroquinone, An aromatic liquid crystal polyester was obtained in the same manner as in Example 1 except that 3.34 g (10 mol%) of 4,4′-dihydroxybiphenyl, 20.08 g of acetic anhydride, and 3.77 mg of potassium acetate were used.
  • the resulting thermoplastic liquid crystal polymer had a melting point of 291 ° C., a solidification temperature of 237 ° C., and a temperature difference between the melting point and the solidification temperature of 54 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • Example 3 The raw materials charged into the reactor were 20.66 g (60 mol%) of 6-hydroxy-2-naphthoic acid, 7.91 g (20 mol%) of 2,6-naphthalenedicarboxylic acid, 3.02 g (15 mol%) of hydroquinone, An aromatic liquid crystal polyester was obtained in the same manner as in Example 1 except that 1.70 g (5 mol%) of 4,4′-dihydroxybiphenyl, 20.55 g of acetic anhydride, and 3.77 mg of potassium acetate were used.
  • the obtained thermoplastic liquid crystal polymer had a melting point of 309 ° C., a solidification temperature of 252 ° C., and a temperature difference between the melting point and the solidification temperature of 57 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer had a melting point of 275 ° C., a solidification temperature of 225 ° C., and a temperature difference between the melting point and the solidification temperature of 50 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • Example 5 The raw materials charged into the reactor were 10.21 g (30 mol%) of 6-hydroxy-2-naphthoic acid, 13.68 g (35 mol%) of 2,6-naphthalenedicarboxylic acid, 3.48 g of hydroquinone (17.5 mol%). ), 4,4′-dihydroxybiphenyl 5.89 g (17.5 mol%), acetic anhydride 20.30 g, and potassium acetate 3.77 mg. It was.
  • the thermoplastic liquid crystal polymer obtained had a melting point of 317 ° C., a solidification temperature of 240 ° C., and a temperature difference between the melting point and the solidification temperature of 77 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • Example 6 The raw materials charged into the reactor were 19.32 g (60 mol%) of 6-hydroxy-2-naphthoic acid, 7.40 g (20 mol%) of 2,6-naphthalenedicarboxylic acid, 3.19 g of 4,4′-dihydroxybiphenyl. (10 mol%), phenylhydroquinone 3.19 g (10 mol%), acetic anhydride 19.21 g, and potassium acetate 3.77 mg were used in the same manner as in Example 1 to obtain an aromatic liquid crystal polyester.
  • the thermoplastic liquid crystal polymer obtained had a melting point of 262 ° C., a solidification temperature of 140 ° C., and a temperature difference between the melting point and the solidification temperature of 122 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • Example 7 The raw materials charged into the reactor were 19.14 g (60 mol%) of 6-hydroxy-2-naphthoic acid, 7.33 g (20 mol%) of 2,6-naphthalenedicarboxylic acid, 3.16 g of 4,4′-dihydroxybiphenyl. (10 mol%), aromatic liquid crystal polyester in the same manner as in Example 1 except that 3.44 g (10 mol%) of 4,4′-dihydroxydiphenyl ether, 19.04 g of acetic anhydride, and 3.77 mg of potassium acetate were used.
  • the resulting thermoplastic liquid crystal polymer had a melting point of 261 ° C., a solidification temperature of 110 ° C., and a temperature difference between the melting point and the solidification temperature of 151 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer had a melting point of 342 ° C., a solidification temperature of 306 ° C., and a temperature difference between the melting point and the solidification temperature of 36 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer had a melting point of 278 ° C., a solidification temperature of 237 ° C., and a temperature difference between the melting point and the solidification temperature of 41 ° C.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer A film was obtained from the obtained thermoplastic liquid crystal polymer by hot pressing, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 5.
  • thermoplastic liquid crystal polymer as a film As shown in Table 5, in Examples 1 to 7, an increase in the melting point can be suppressed, and the temperature difference between the melting point and the solidification temperature can be increased. Furthermore, the dielectric loss tangent at 5 GHz of the obtained thermoplastic liquid crystal polymer as a film is extremely low.
  • the comparative example 1 which is a thermoplastic liquid crystal polymer composition of the Example of patent document 1 does not contain the repeating unit represented by Formula (II), and contains many repeating units derived from another dicarboxylic acid (terephthalic acid). Because of the composition, the dielectric loss tangent at 5 GHz in the film is more than twice that of the example. Furthermore, although the comparative example 1 contains two types of repeating units derived from aromatic diol, since those molar ratios are not in a specific range, the melting point is high.
  • Comparative Example 2 does not include the repeating unit represented by the formula (II) and the content of the repeating unit having a naphthalene skeleton is small, the dielectric loss tangent at 5 GHz in the film is more than three times that of the example. .
  • Comparative Example 3 is a composition containing repeating units represented by Formula (I) and Formula (II), the dielectric loss tangent at 5 GHz in the film is as low as that of the Example. However, although it contains two types of repeating units derived from aromatic diols, the melting point is high because their molar ratio is not within a specific range.
  • Comparative Example 4 is a composition containing repeating units represented by Formula (I) and Formula (II), the dielectric loss tangent at 5 GHz in the film is equivalent to that of the Example. However, since it contains only one type of repeating unit derived from an aromatic diol, the melting point is high.
  • the dielectric loss tangent at 24 GHz which is a higher frequency band, is also low.
  • the increase in dielectric loss tangent can be suppressed even at high temperatures (120 ° C.) where the dielectric loss tangent increases due to dielectric loss that increases as the temperature increases. .
  • the dielectric loss tangent at 24 GHz which is a higher frequency band, is more than three times that of the example. Further, the increase in dielectric loss tangent cannot be suppressed even at high temperatures (120 ° C.).
  • thermoplastic liquid crystal polymer of the present invention can provide a film having a very small dielectric loss tangent
  • the thermoplastic liquid crystal polymer film obtained by molding the thermoplastic liquid crystal polymer can be used for a substrate material, particularly a radar corresponding to the gigahertz band. It can be suitably used as a substrate material to be used.

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PCT/JP2018/012219 2017-03-31 2018-03-26 熱可塑性液晶ポリマーおよびそのフィルム WO2018181222A1 (ja)

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JP2019509835A JP7069124B2 (ja) 2017-03-31 2018-03-26 熱可塑性液晶ポリマーおよびそのフィルム
EP18778136.4A EP3604381B1 (en) 2017-03-31 2018-03-26 Thermoplastic liquid crystal polymer and film of same
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JP2020193261A (ja) * 2019-05-27 2020-12-03 上野製薬株式会社 液晶ポリマー組成物
CN114402055A (zh) * 2019-09-10 2022-04-26 提克纳有限责任公司 包含聚合物组合物的5g系统
CN114729262A (zh) * 2019-09-10 2022-07-08 提克纳有限责任公司 用于5g应用的聚合物组合物和薄膜
EP4028486A4 (en) * 2019-09-10 2023-11-15 Ticona LLC 5G SYSTEM CONTAINING A POLYMER COMPOSITION
EP4035266A4 (en) * 2019-09-23 2023-11-01 Ticona LLC RF FILTER FOR USE AT 5G FREQUENCIES
US11608410B2 (en) 2019-12-23 2023-03-21 Chang Chun Plastics Co., Ltd. Liquid crystal polymer film and laminate comprising the same
US11840602B2 (en) 2019-12-23 2023-12-12 Chang Chun Plastics Co., Ltd. Laminate, circuit board, and liquid crystal polymer film applied to the same
US11926698B2 (en) 2019-12-23 2024-03-12 Chang Chun Plastics Co., Ltd. Liquid crystal polymer film and laminate comprising the same
US11945907B2 (en) 2019-12-23 2024-04-02 Chang Chun Plastics Co., Ltd. Liquid crystal polymer film and laminate comprising the same
US12103285B2 (en) 2019-12-23 2024-10-01 Chang Chun Plastics Co., Ltd. Liquid crystal polymer film and laminate comprising the same
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